Controlling Surface Structure and Primary Particle Size to Enhance Performance and Reduce Gas Evolution in Lithium- and Manganese-Rich Layered Oxide Cathodes.

Practical application of lithium- and manganese-rich layered oxide cathodes has been hindered despite their high performance and low cost owing to high gas evolution accompanying capacity loss even in a conservative voltage window. Here, we control the surface structure and primary particle size of lithium- and manganese-rich layered oxide cathodes not only to enhance the electrochemical performance but also to reduce gas evolution. Sulfur-coated Fm3̅m/R3̅m double reduced surface layers and Mo doping dramatically reduce gas evolution, which entails the improvement of electrochemical performance. With the optimization, we prove that it is competitive enough to conventional high-nickel cathodes in the aspects of gas evolution as well as electrochemical performance in the conservative voltage window of 2.5-4.4 V. Our findings provide invaluable insights on the improvement of electrochemical performance and gas evolution properties in lithium- and manganese-rich layered oxide cathodes.

Bioelectrical Nose Platform Using Odorant-Binding Protein as a Molecular Transporter Mimicking Human Mucosa for Direct Gas Sensing.

Recently, various bioelectronic nose devices based on human receptors were developed for mimicking a human olfactory system. However, such bioelectronic nose devices could operate in an aqueous solution, and it was often very difficult to detect insoluble gas odorants. Here, we report a portable bioelectronic nose platform utilizing a receptor protein-based bioelectronic nose device as a sensor and odorant-binding protein (OBP) as a transporter for insoluble gas molecules in a solution, mimicking the functionality of human mucosa. Our bioelectronic nose platform based on I7 receptor exhibited dose-dependent responses to octanal gas in real time. Furthermore, the bioelectronic platforms with OBP exhibited the sensor sensitivity improved by ∼100% compared with those without OBP. We also demonstrated the detection of odorant gas from real orange juice and found that the electrical responses of the devices with OBP were much larger than those without OBP. Since our bioelectronic nose platform allows us to directly detect gas-phase odorant molecules including a rather insoluble species, it could be a powerful tool for versatile applications and basic research based on a bioelectronic nose.

Artificial Adaptive and Maladaptive Sensory Receptors Based on a Surface-Dominated Diffusive Memristor.

A biological receptor serves as sensory transduction from an external stimulus to an electrical signal. It allows humans to better match the environment by filtering out repetitive innocuous information and recognize potentially damaging stimuli through key features, including adaptive and maladaptive behaviors. Herein, for the first time, the authors develop substantial artificial receptors involving both adaptive and maladaptive behaviors using diffusive memristor. Metal-oxide nanorods (NR) as a switching matrix enable the electromigration of an active metal along the surface of the NRs under electrical stimulation, resulting in unique surface-dominated switching dynamics with the advantage of fast Ag migration and fine controllability of the conductive filament. To experimentally demonstrate its potential application, a thermoreceptor system is constructed using memristive artificial receptors. The proposed surface-dominated diffusive memristor allows the direct emulation of the biological receptors, which represents an advance in the bioinspired technology adopted in creating artificial intelligence systems.

Electric-field control of field-free spin-orbit torque switching via laterally modulated Rashba effect in Pt/Co/AlOx structures.

Spin-orbit coupling effect in structures with broken inversion symmetry, known as the Rashba effect, facilitates spin-orbit torques (SOTs) in heavy metal/ferromagnet/oxide structures, along with the spin Hall effect. Electric-field control of the Rashba effect is established for semiconductor interfaces, but it is challenging in structures involving metals owing to the screening effect. Here, we report that the Rashba effect in Pt/Co/AlOx structures is laterally modulated by electric voltages, generating out-of-plane SOTs. This enables field-free switching of the perpendicular magnetization and electrical control of the switching polarity. Changing the gate oxide reverses the sign of out-of-plane SOT while maintaining the same sign of voltage-controlled magnetic anisotropy, which confirms the Rashba effect at the Co/oxide interface is a key ingredient of the electric-field modulation. The electrical control of SOT switching polarity in a reversible and non-volatile manner can be utilized for programmable logic operations in spintronic logic-in-memory devices.

Non-Equilibrium Sodiation Pathway of CuSbS2.

Binary metal sulfides have been explored as sodium storage materials owing to their high theoretical capacity and high stable cyclability. Nevertheless, their relative high charge voltage and relatively low practical capacity make them less attractive as an anode material. To resolve the problem, addition of alloying elements is considerable. Copper antimony sulfide is investigated as a representative case. In this study, we do not only perform electrochemical characterization on CuSbS2, but also investigate its nonequilibrium sodiation pathway employing in-/ex situ transmission electron microscopy, in situ X-ray diffraction, and density functional theory calculations. Our finding provides valuable insights on sodium storage into ternary metal sulfide including an alloying element.

Publisher Correction: Distinct handedness of spin wave across the compensation temperatures of ferrimagnets.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Lithographically patterned well-type graphene liquid cells with rational designs.

Graphene liquid cell transmission electron microscopy allows in situ observation of nanomaterial dynamics in a liquid environment. However, this method suffers from both random formation and small size of liquid pockets. Here, we introduce facile and mass-producible graphene-sealed well-type liquid cells with rational designs. The developed liquid cell structure and its formation mechanism depending on hole diameter (d)/spacer thickness (h) ratio are systematically analyzed. Finally, we show its high-resolution imaging and chemical analysis capability for nanoparticles and biomaterial applications. This work will provide an enhanced liquid cell platform for diverse liquid environmental studies.

Distinct handedness of spin wave across the compensation temperatures of ferrimagnets.

Antiferromagnetic spin waves have been predicted to offer substantial functionalities for magnonic applications due to the existence of two distinct polarizations, the right-handed and left-handed modes, as well as their ultrafast dynamics. However, experimental investigations have been hampered by the field-immunity of antiferromagnets. Ferrimagnets have been shown to be an alternative platform to study antiferromagnetic spin dynamics. Here we investigate thermally excited spin waves in ferrimagnets across the magnetization compensation and angular momentum compensation temperatures using Brillouin light scattering. Our results show that right-handed and left-handed modes intersect at the angular momentum compensation temperature where pure antiferromagnetic spin waves are expected. A field-induced shift of the mode-crossing point from the angular momentum compensation temperature and the gyromagnetic reversal reveal hitherto unrecognized properties of ferrimagnetic dynamics. We also provide a theoretical understanding of our experimental results. Our work demonstrates important aspects of the physics of ferrimagnetic spin waves and opens up the attractive possibility of ferrimagnet-based magnonic devices.

Direct Visualization of Lithium Polysulfides and Their Suppression in Liquid Electrolyte.

Understanding of lithium polysulfide (Li-PS) formation and the shuttle phenomenon is essential for practical application of the lithium/sulfur (Li/S) cell, which has superior theoretical specific energy (2600 Wh/kg). However, it suffers from the lack of direct observation on behaviors of soluble Li-PS in liquid electrolytes. Using in situ graphene liquid cell electron microscopy, we have visualized formation and diffusion of Li-PS simultaneous with morphological and phase evolutions of sulfur nanoparticles during lithiation. We found that the morphological changes and Li-PS diffusion are retarded by ionic liquid (IL) addition into electrolyte. Chronoamperometric shuttle current measurement confirms that IL addition lowers the experimental diffusion coefficient of Li-PS by 2 orders of magnitude relative to that in IL-free electrolyte and thus suppresses the Li-PS shuttle current, which accounts for better cyclability and Coulombic efficiency of the Li/S cell. This study provides significant insights into electrolyte design to inhibit the polysulfide shuttle phenomenon.

Graphene Liquid Cell Electron Microscopy of Initial Lithiation in Co3O4 Nanoparticles.

As it governs the overall performance of lithium-ion batteries, understanding the reaction pathway of lithiation is highly desired. For Co3O4 nanoparticles as anode material, here, we report an initial conversion reaction pathway during lithiation. Using graphene liquid cell electron microscopy (GLC-EM), we reveal a CoO phase of the initial conversion product as well as morphological dynamics during Co3O4 lithiation. In accordance with the in situ TEM observation, we confirmed that the Co3O4 to CoO conversion is a thermodynamically favorable process by calculating the theoretical average voltage based on density functional theory. Our observation will provide a useful insight into the oxide electrode that undergoes conversion reaction.

Strong stress-composition coupling in lithium alloy nanoparticles.

The stress inevitably imposed during electrochemical reactions is expected to fundamentally affect the electrochemistry, phase behavior and morphology of electrodes in service. Here, we show a strong stress-composition coupling in lithium binary alloys during the lithiation of tin-tin oxide core-shell nanoparticles. Using in situ graphene liquid cell electron microscopy imaging, we visualise the generation of a non-uniform composition field in the nanoparticles during lithiation. Stress models based on density functional theory calculations show that the composition gradient is proportional to the applied stress. Based on this coupling, we demonstrate that we can directionally control the lithium distribution by applying different stresses to lithium alloy materials. Our results provide insights into stress-lithium electrochemistry coupling at the nanoscale and suggest potential applications of lithium alloy nanoparticles.

Pulverization-Tolerance and Capacity Recovery of Copper Sulfide for High-Performance Sodium Storage.

Finding suitable electrode materials is one of the challenges for the commercialization of a sodium ion battery due to its pulverization accompanied by high volume expansion upon sodiation. Here, copper sulfide is suggested as a superior electrode material with high capacity, high rate, and long-term cyclability owing to its unique conversion reaction mechanism that is pulverization-tolerant and thus induces the capacity recovery. Such a desirable consequence comes from the combined effect among formation of stable grain boundaries, semi-coherent boundaries, and solid-electrolyte interphase layers. The characteristics enable high cyclic stability of a copper sulfide electrode without any need of size and morphological optimization. This work provides a key finding on high-performance conversion reaction based electrode materials for sodium ion batteries.

Morphological Evolution Induced through a Heterojunction of W-Decorated NiO Nanoigloos: Synergistic Effect on High-Performance Gas Sensors.

Morphological evolution accompanying a surface roughening and preferred orientation is an effective way to realize a high-performance gas sensor because of its significant potential as a chemical catalyst through chemical potentials and atomic energy states. In this work, we investigated a heterojunction of double-side-W-decorated NiO nanoigloos fabricated through radio frequency sputtering and a soft-template method. Interestingly, a morphological evolution characterized by a pyramidal rough surface and the preferred orientation of the (111) plane was observed upon decorating the bare NiO nanoigloos with W. The underlying mechanism of the morphological evolution was precisely demonstrated based on the van der Drift competitive growth model originating from the oxygen transport and chemical strain in the lattice. The gas sensing properties of W-decorated NiO show an excellent NO2 response and selectivity when compared to other gases. In addition, high response stability was evaluated under interference gas and humidity conditions. The synergistic effects on the sensing performance were interpreted on the basis of the morphological evolution of W-decorated NiO nanoigloos.

Atomic visualization of a non-equilibrium sodiation pathway in copper sulfide.

Sodium ion batteries have been considered a promising alternative to lithium ion batteries for large-scale energy storage owing to their low cost and high natural abundance. However, the commercialization of this device is hindered by the lack of suitable anodes with an optimized morphology that ensure high capacity and cycling stability of a battery. Here, we not only demonstrate that copper sulfide nanoplates exhibit close-to-theoretical capacity (~560 mAh g-1) and long-term cyclability, but also reveal that their sodiation follows a non-equilibrium reaction route, which involves successive crystallographic tuning. By employing in situ transmission electron microscopy, we examine the atomic structures of four distinct sodiation phases of copper sulfide nanoplates including a metastable phase and discover that the discharge profile of copper sulfide directly reflects the observed phase evolutions. Our work provides detailed insight into the sodiation process of the high-performance intercalation-conversion anode material.

Nanoscale hybrid systems based on carbon nanotubes for biological sensing and control.

This paper provides a concise review on the recent development of nanoscale hybrid systems based on carbon nanotubes (CNTs) for biological sensing and control. CNT-based hybrid systems have been intensively studied for versatile applications of biological interfaces such as sensing, cell therapy and tissue regeneration. Recent advances in nanobiotechnology not only enable the fabrication of highly sensitive biosensors at nanoscale but also allow the applications in the controls of cell growth and differentiation. This review describes the fabrication methods of such CNT-based hybrid systems and their applications in biosensing and cell controls.

Direct mapping of electrical noise sources in molecular wire-based devices.

We report a noise mapping strategy for the reliable identification and analysis of noise sources in molecular wire junctions. Here, different molecular wires were patterned on a gold substrate, and the current-noise map on the pattern was measured and analyzed, enabling the quantitative study of noise sources in the patterned molecular wires. The frequency spectra of the noise from the molecular wire junctions exhibited characteristic 1/f2 behavior, which was used to identify the electrical signals from molecular wires. This method was applied to analyze the molecular junctions comprising various thiol molecules on a gold substrate, revealing that the noise in the junctions mainly came from the fluctuation of the thiol bonds. Furthermore, we quantitatively compared the frequencies of such bond fluctuations in different molecular wire junctions and identified molecular wires with lower electrical noise, which can provide critical information for designing low-noise molecular electronic devices. Our method provides valuable insights regarding noise phenomena in molecular wires and can be a powerful tool for the development of molecular electronic devices.

"Bio-switch Chip" Based on Nanostructured Conducting Polymer and Entrapped Enzyme.

We report a switchable biochip strategy where enzymes were entrapped in conducting polymer layers and the enzymatic reaction of the entrapped enzymes was controlled in real-time via electrical stimuli on the polymer layers. This device is named here as a "bio-switch chip" (BSC). We fabricated BSC structures using polypyrrole (Ppy) with entrapped glucose oxidase (GOx) and demonstrated the switching of glucose oxidation reaction in real-time. We found that the introduction of a negative bias voltage on the BSC structure resulted in the enhanced glucose oxidation reaction by more than 20 times than that without a bias voltage. Moreover, because the BSC structures could be fabricated on specific regions, we could control the enzymatic reaction on specific regions. In view of the fact that enzymes enable very useful and versatile biochemical reactions, the ability to control the enzymatic reactions via conventional electrical signals could open up various applications in the area of biochips and other biochemical industries.

Magnetically-refreshable receptor platform structures for reusable nano-biosensor chips.

We developed a magnetically-refreshable receptor platform structure which can be integrated with quite versatile nano-biosensor structures to build reusable nano-biosensor chips. This structure allows one to easily remove used receptor molecules from a biosensor surface and reuse the biosensor for repeated sensing operations. Using this structure, we demonstrated reusable immunofluorescence biosensors. Significantly, since our method allows one to place receptor molecules very close to a nano-biosensor surface, it can be utilized to build reusable carbon nanotube transistor-based biosensors which require receptor molecules within a Debye length from the sensor surface. Furthermore, we also show that a single sensor chip can be utilized to detect two different target molecules simply by replacing receptor molecules using our method. Since this method does not rely on any chemical reaction to refresh sensor chips, it can be utilized for versatile biosensor structures and virtually-general receptor molecular species.